Composition protecting against the action of microorganisms and its manner of use

ABSTRACT

THE INVENTION PREVENTS DAMAGE TO LIQUID OR WET PAPER PULP BY MICROORGANISMS AND FORESTALS OR DESTROYS THE MICROBIC OOZE THAT FORMS IN THE WATER OF SYSTEMS OF PAPER MILLS BY USE OF A COMPOSITION COMPRISING A MIXTURE OF (1) ALKALI METAL OR ALKALINE EARTH METAL SALTS OF DI (LOWER ALKYL) DITHIOCARBAMIC ACID, CHIEFLY ALKALI METAL DIMETHYL DITHIOCARBAMATE, (3) ALKALI METAL OF (LOWER ALKYLENE)BIS-DITHIOCARBAMIC ACID, CHIEFLY (ETHYLENE) -BIS-DITHIOCARBAMIC ACID, AND (3) A STABILIZER CONSISTING OF 1,8,3,6 DIENDOMETHYLENE 1,3,6,8 TETRAAZACYCLODECANE, ALSO KNOWN AS 1,3,6,8 DIENDOMETHYLENE 1,3,6,8 TETRAAZACYCLODECANE.

United States Patent Int. Cl. Aoln 9/02 US. Cl. 424-286 6 Claims ABSTRACT OF THE DISCLOSURE The invention prevents damage to liquid or wet paper pulp by microorganisms and forestalls or destroys the microbic ooze that forms in the water of systems of paper mills by use of a composition comprising a mixture of (1) alkali metal or alkaline earth metal salts of di(lower alkyl) dithiocarbamic acid, chiefly alkali metal dimethyl dithiocarbamate, (2) alkali metal of (lower alkylene)- bis-dithiocarbamic acid, chiefly (ethylene) bis dithiocarbamic acid, and (3) a stabilizer consisting of l,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane, also known as l,3,6,8 diendomethylene 1,3,6,8 tetraazacyclodecane.

This application is a continuation-impart of our copending application Ser. No. 318,440, filed Oct. 23, 1962, now abandoned, in the names of Jean-Paul Pelissier and Pierre Chitfert.

This invention relates, by way of a new product, to a composition for protecting all industrial products liable to biological deterioration. In particular, the invention prevents damage to liquid or wet paper pulp by microorganisms and forestalls or destroys the microbic ooze that forms in the water systems of paper mills. The invention also relates to the manner or methods of industrially using the composition.

In the manufacture of paper, large losses often result from the fermentation of wet cellulosic pulp. In addition, it is well known that the growth of various bacterial or fungal microorganisms presents serious problems in the manufacture of paper. Microorganisms cause the formation of microbic ooze in the water systems, resulting in clogging of the piping and in causing the band of paper either to break or to weaken, resulting in disruptions in the manufacture and a decline in the production.

To eliminate these drawbacks, various chemicals have been used, such as first chloramin, phenols, and chlorophenols, on the one hand, which have not given the anticipated results, and second organo-mercurial compounds, on the other hand, which have been most satisfactory, except for the drawback, among others, that they are toxic. It has been necessary, consequently, to pursue further research to find compositions that are efficacious but non-toxic.

The fungicidal and bactericidal properties of dithiocarbamates, certain of which are widely used in agriculture as anti-cryptogamous agents, in the form of insoluble salts of various metals, have long been known.

During their research, the inventors made the following unexpected discovery forming the basis of the invention: biological damage to industrial products, and particularly with regard to paper making treatments (damage to pulp, prevention or destruction of microbic ooze), can be avoided in a way that is at once advantageous and thorough by treating the products with a stabilized or unstabilized mixture of water soluble salts of at least one mono or dialkyl dithiocarbamic acid and of an alkylene-bis-dithiocarbamic acid. The soluble salts are particularly alkaline or alkaline earth salts, including ammonium or quaternary ammonium salts; the alkyl radical comprises one to three carbon atoms, and the alkylene comprises two or three carbon atoms. It has been found that the effectiveness of such a mixture is at least equal, and usually superior, to that of each of its parts taken separately. In other words, for reasons and in a way not yet clearly understood, the simple mixture of the two kinds of dithiocarbamates mentioned above causes a reciprocal reinforcement of their effects. It is observed that the compositions of the invention, when used for the purposes indicated, give rise to numerous advantages alongside their non-toxicness. 0n the one hand, the compositions do not leave toxic residues. On the other hand, the range of activity on the different bacterial or cryptogamous organisms is broadened. The action of the compositions increases normally with their concentration in the mass treated; that is, there are no inversion zones as there are with the constituents taken alone (the behavior of sodium dimethylthiocarbamate being well known).

The ingredients of the mixtures are: (l) Alkyl dithiocarbamates having the formula where:

R is an alkyl group having a low molecular weight (equal to or less than C R is H or an alkyl group of low molecular weight; and

M is an alkaline or an alkaline earth cation or a quaternary ammonium; and

(2) alkylene-bis-dithiocarbamates having the formula MS-C--NH(CH2)nNHCSM l t where n is equal to 2 or to 3 and M has the same meaning as under (1). l

The soluble salts of ethylene-bis-dithiocarbamic acid have shown themselves particularly advantageous within the scope of the invention.

A composition, which is especially effective, is a mixture of alkaline-dimethyldithiocarbamate and ethylene alkaline-bis-dithiocarbamate, the molecular proportions being varied from five to one or one to five.

The compositions obtained from the mixture are solutions that are generally stable under normal conditions for from two to six months. According to another object of the invention, their stability can be improved by adding the condensation product of ethylenediamine with methanal. Said product was prepared by Bischoif (Berichte 3l-32541898). The quantity added may amount to 25 of the dithiocarbamic salts. It is interesting to observe that, even in the very large quantities indicated, the weak action of the stabilizer has no unfavorable elfect on the activity of the composition.

A composition containing 10% to 25% of this additive remains stable for from 18 to 24 months under usual conditions.

The compositions of the invention are employed as aqueous solutions. They can be prepared either by mixing aqueous solutions of the various components of the composition, according the desired proportions, or by operating the reaction from a mixture of amines.

There will now be given a number of detailed examples of compositions of the invention, with the results obtained from their use compared with those obtained from the individual constituents.

EXAMPLE 1 632 grams of 40% dimethylamine solution, 415 grams of 20% ethylenediamine solution, and 1090 grams of 30% caustic soda lye were loaded into a glass reactor furnished with means for agitation and reflux.

While agitating and cooling, 632 grams of carbon disulphide were then added. The temperature was held to 28 C. :1 C.

The addition took about one hour, and the temperature was held for two more hours. 2300 milliliters of a yellowish-reddish solution, having density of 1.2, were obtained.

Analysis (Roth method) showed that the content of carbon disulphide combined in the form of dithiocarbamates was 21.9% by weight.

The composition of the invention can also be obtained by mixing corresponding amounts of solutions of sodium dimethyldithiocarbamate and sodium ethylene-bis-dithiocarbamate.

EXAMPLE 2 The procedure of Example 1 was followed, using the following chemicals:

G. 40% dimethylamine 168 92% ethylenediamine 28 35% monomethylamine 24 30% solution of sodium hydroxide 345 Water 239 Carbon disulphide 196 The 1000 grams of the resulting product revealed on analysis that there was (18.8:4) by weight of carbon disulphide combined in the form of sodium dithiocarbamates.

The amine proportions can be varied. Broadly, from 0.2 to 0.5 of a mole of ethylenediamine are preferably used for from 0.8 to 0.5 of a mole of alkylamine.

The compositions Examples 1 and 2 remained stable for 12 weeks.

EXAMPLE 3 Twenty-five parts of a 40% aqueous solution of 1,3,6,8 diendomethylene l,3,6,8 tetraazacyclodecane 1,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane assigned the following formula were added to 75 parts of the solution obtained in Example 1.

The 1,3,6,8 diendomethylene 1,3,6,8 tetraazacyclodecane or 1,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane had been prepared by the action of ethylenediamine on formaldehyde in aqueous solution.

It is not necessary to separate the product from its solution, which can be directly mixed with the solution of Example 1.

Diendomethylene tetraazacyclodecane can be prepared as follows:

In a reactor provided with a reflux cooler, one has loaded a solution of 115 kg. of 30% formal; one has slowly poured into 35 kg. of 92% ethylenediamine, while the apparatus was cooled through water flow to hold the mixture at a temperature from 28 C.-30 C. The reaction was pursued for one hour and one has then heated slowly to 48-50 C.

The clear yellow soltuion has pH equal to 8.7.

4 EXAMPLE 4 In one proceeding there has been prepared as follows a composition containing the mixture of dithiocarbamates and diendomethylenetetraazacyclodecane:

7.7 kg. of 30% formal having been loaded in a rustless steel reactor of liters, provided with means for reflux". On another part, there has been prepared a mixture of:

Kg. 30% soda lye 1.9 Water 3.3 92% ethylenediamine 2.4

Said solution has been poured into the formal under cooling with holding the temperature at 28 C.30 C. One has then heated further to 30 C.

One has cooled to 20 C. and there has been added:

Water 6.9

40% diethylamine 20.6

92% ethyldiamine 3 Then, one has introduced slowly:

Carbon sulphide 5.125

Soda lye 8.425

The successive addition of carbon sulphide and soda lye has been repeated three times (at all, 4 additions); the temperature was 28 C.

The solution obtained was yellow-green, with a density 1.185 and containing 20% of combined carbon sulphide.

COMPARATIVE BIOLOGICAL TESTS The bacteriostatic threshold (the amount inhibiting growth in culture broth) and the bactericidal threshold (destruction in an agar-agar containing nutritive medium) were determined. Following a similar method, the fungistatic thresholds were also found.

The tests were conducted on a broad range of microorganisms, among which were a mushroom (Aspergillus flavus), a Gram-positive bacterium (Staphylococcus aureus), and a Gram-negative bacterium (Pseudomonas aeruginosa) The tables show some of the results obtained with the products used.

In the tables, PR and PR respectively designate the compositions of Examples 1 and 3. The amounts of active substances are given in parts per million (ppm).

Tables Ia Ib relate to the fungicidal and fungistatic thresholds on Aspergillus flavus.

TABLE Ia.FUNGISTATIC TEST Concentration in p.p.m. oi

active substance 48 hours after 144 hours after Substance contamination contamination PR1 0 0 0 3 0 0 5 Sodium dlmethyl-dithiocarbamate 0 0 2 5 0 0 6 Sodium ethylene-bis-dithiocarbamate. 0 0 0 6 0 1 b Norm-Control culture: 5 and 5.

Tables H and III show the bacteriostatic and bacteri- (DMTCD). No control is obtained with product A. At cidal levels, respectively, with Staphylococcus aureus. p.p.m., the product B gives total control. The synergism A. STAPHYLOCOCCUS AUREUS is evident- Substance 40 20 10 5 1 0.1

PR1 0 0 0 0 Slight cloudiness Sodium dimethyldithiocarbamate.. 0 0 0 0 One-halt of control culture Sodium ethylene-bis-dithiocarbamate. 0

l Control culture: strong growth.

B. PSEUDOMONAS AERUGINOSA TABLE v TABLE IIIa.BACTERIOSTATIC TEST Concentra- Millions of microorganisms per tion in p.p.m. milliliter of fibrous suspension Concentration in p.p.m. of active (dry matesubstance rial) 1st day 2nd day 3rd day Substance 400 200 10 a0 1 1315 70.0 75.15 Product A 5 77. 0 90. 0 93. 5 PR1 0 0 0 .5 82.0 70.0 Sodium dimethyl-di- 0 .0 96.5 112.5 thiocarbamate. Product B.. 0 87. 0 75.0 Sodium ethylene-bls- 0 E of control culture. 0 0 0 dithiocarbamate. Control 1. .5 88. 5 93. 5 Control 2... 100. 0 86. 0 97. 5 1 Control culture: strong growth.

TABLE IITD.BACTERICIDAL TEST Concentration in p.p.m. of active substance Substance 800 600 400 200 100 so PR|.- 0 0 0... 0 Moteontrol culture. Sodium dimethyl-di- 0 0 thiocarbamate. Sodium ethylene-bis- 0 $4 of control culture. }6 of control culture.

dithiocarbamate.

l Control culture: strong growth.

In another series of tests, realized in a different manner, It will be noted that the effect of an aqueous solution one has first developed a culture of Aerobacter aerogenes of DMTCD (1,3,6,8 diendomethylene l,3,6,8 tetraazacyon a meat broth and in its maximal phase of growth, one clodecane) was also investigated. has seeded a new medium and efiected the treatment with These results are strong evidence of the remarkable the products being at the desired concentration. The peraction of the compositions of the invention, in comparison cent of mortality has been tested relatively to the concenwith those obtained from the individual constituents and tration of active material. One has obtained the curves the stabilizer. shown in the annnexed drawing (with the concentrations Finally, two ways of employing the compositions of the in abscissae and the mortality in ordinates), respectively invention will be given by way of illustration. for product PR sodium dimethyldithiocarbamate (I) and ethylene-bis-dithiocarbamate (II). EXAMPLE 4 The difierent constituents and compositions were tested The daily number of breaks was ten for a machine and compared under practical conditions, using a subproducing 200 kilograms of newsprint daily in a paper stratum of pulp first seeded with Aerobacter aerogenes. factory.

The results are arranged in Table IV. The ooze formed chiefly in the head box, in the slots TABLE IV Millions of microorganisms per Concenmilliliter of fibrous suspension, hours tratlon Substance in p.p.m. 24 48 72 144 PR; 5 0 0 0 0 10 0 0 0 0 25 0 0 0 0 50 0 0 0 0 Sodium di-methyl-di-thicearbamate 5 0. 130 119. 50 244. 00 42. 00 10 0 0 111.90 85.00 25 0 o 0 0 50 0 0 0 0 Sodium ethylene-bis-dithio-carbamate. 5 32. 35 136. 50 126. 50 32. 50 10 e 00 126.50 143. 50 26.50 25 0 0 0 0 50 0 0 0 0 PR3 5 0 0 0 0 10 0 0 0 0 25 0 0 0 0 50 0 0 0 0 DMTCD 5 38.20 104.50 154 29 10 21.65 111.00 118 37 25 20. 05 100.50 148 54 50 0 0 0 0 Control Suspension 1 25. 64 85. 15 50 21. 50 24. 24 140.50 50 21.10

Control Suspension 2 In Table V, below, which is similar to Table IV, the of the Lamor screens, and on the walls of the back water product A consists of ethylene-bis-dithiocar-bamate and dibox. methyl dithiocarbamate. The product B consists of product The PR 3 mixture was continuously added in the Four- A+diendomethylene tetraazacyclodecane as stabilizer 75 drinier pit catching the water from the pulp, so that its concentration in the water was from O.2-to 1 p.p.m. The average number of breaks over a period of 15 days was reduced to one or two daily. Moreover, it must be noted that it was impossible to be certain that these breaks were caused by the formation of ooze.

EXAMPLE In a paper factory using a Kraft paper machine producing 500 kilograms per day, the recycled water having a pH of 6.5 to 7, it was necessary to shut down the machine once every two days to clean the head water system of the machine. Adding the PR 3 mixture by means of the pulp dilution pump, at the rate of 1 to 3 p.p.m., completely eliminated any need for this cleaning.

We claim:

1. A bacteriostatic and bactericidal composition consisting essentially of (1) a water soluble salt selected from the group consisting of alkali metal and alkaline earth metal salts of alkyl dithiocarbamic acids, the alkyl group being of one to three carbon atoms, (2) a water soluble salt selected from the group consisting of alkali metal and alkaline earth metal salts of alkylene-bis-dithiocarbamic acids, the alkylene radical being of two to three carbon atoms, and (3) a stabilizer consisting essentially of 1,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane, the molecular proportions between the alkyl dithiocarbamate and the alkylene-bis-dithiocarbamate varying from one to five and five to one by weight and the stabilizer being from to 25% of the weight of the composition.

2. The composition of claim 1, wherein the alkyl dithiocarbamate is of the formula where R is an alkyl group equal to or less than C R' is H or an alkyl group equal to or less than C and M is an alkali or alkaline earth metal substituent.

3. The composition of claim 1, wherein the alkylenebis-dithiocarbamate is of the formula where n is two or three and M is alkali or alkaline earth metal substituent.

4. The composition of claim 2, wherein the alkylene-bisdithiocarbamate is of the formula where n is two or three and M is as in claim 2.

5. The composition of claim 3, wherein a soluble salt of ethylene-bis-dithiocarbamic acid is employed.

6. The composition of claim 4, wherein there is a mixture of dimethyl dithiocarbamate and of ethylene-alkali metal-bis-dithiocarbamate.

References Cited OTHER REFERENCES Reddish (Antiseptics, Disenfectants, Fungicides and Chemical and Physical Sterilization, Lea and Febiger, Philadelphia, 1954, pp. 628-630).

American Chemical Society, 77 (1955 pp. 3157-3159.

ALBERT T. MYERS, Primary Examiner F. E. WADDELL, Assistant Examiner 

